O 1s excitation and ionization processes in the CO2 molecule studied via detection of low-energy fluorescence emission

Oxygen 1s excitation and ionization processes in the CO2 molecule have been studied with dispersed and non-dispersed fluorescence spectroscopy as well as with the vacuum ultraviolet (VUV) photon?photoion coincidence technique. The intensity of the neutral O emission line at 845 nm shows particular sensitivity to core-to-Rydberg excitations and core?valence double excitations, while shape resonances are suppressed. In contrast, the partial fluorescence yield in the wavelength window 300?650 nm and the excitation functions of selected O+ and C+ emission lines in the wavelength range 400?500 nm display all of the absorption features. The relative intensity of ionic emission in the visible range increases towards higher photon energies, which is attributed to O 1s shake-off photoionization. VUV photon?photoion coincidence spectra reveal major contributions from the C+ and O+ ions and a minor contribution from C2+. No conclusive changes in the intensity ratios among the different ions are observed above the O 1s threshold. The line shape of the VUV?O+ coincidence peak in the mass spectrum carries some information on the initial core excitation

Effects of irrigation and time of application on the yield and quality of cv. Cabernet sauvignon in a warm climate

Mediterranean climate is characterized by hot summer, high evapotranspiration rates, and scarce precipitations (400 mm per year) during grapevine cycle. These extremely dry conditions affect vineyard productivity and sustainability. Supplementary irrigation is a needed practice in order to maintain yield and quality. Almost all Spanish grape growing regions are characterized by these within this context, especially in the center region, where this study was performed. The main objective of this work was to study the influence of irrigation on yield and quality. For this aim, we applied different levels of irrigation (mm of water applied) during different stages of growth and berry maturity. Four experimental treatments were applied considering the amount of water and the moment of the application: T1: Water irrigation (420 mm) applied from bloom to maturity. T2: Corresponded to the traditional irrigation scheduling, from preveraison to maturity (154 mm). T3: Water irrigation from bloom to preveraison, and water deficit from veraison to maturity (312 mm). T4: Irrigation applied from preveraison to maturity (230 mm) Experimental vineyard, cv. Cabernet Sauvignon, was located in a commercial vineyard (Bodegas Licinia S.L.) in the hot region of Morata de Tajuña (Madrid). The trial was performed during 2010 and 2011 seasons. Our results showed that yield increased from 2010 to 2011 in the treatments with a higher amount of water appli ed, T1 and T3 (24 and 10 % of yield increase respectively). This was mainly due to an increase in bud fertility (nº of bunches per shoot). Furthermore, sugar content was higher in T3 (27.3 ºBrix), followed by T2 (27 ºBrix). By contrast, T4 (irrigation from veraison) presented the lowest solid soluble concentration and the highest acidity. These results suggest that grapevine has an intrinsic capacity to adapt to its environment. However, this adaptation capacity should be evaluated considering the sensibility of quality parameters during the maturity period (acidity, pH, aroma, color...) and its impact on yield. Here, we demonstrated that a higher amount of water irrigation applied was no linked to a negative effect on quality.

On the production of N-2(+) ions at the N 1s edge of the nitrogen molecule

The N+2 ion yield of the N2 molecule has been measured at the N 1s → Rydberg excitations. It displays Fano-type line shapes due to interference between direct outer-valence photoionization and participator decay of the core-excited Rydberg states. The N+2 ion yield is compared with the total intensity of the outer-valence photoelectron lines obtained recently with electron spectroscopy (Kivimäki et al 2012 Phys. Rev. A 86 012516). The increasing difference between the two curves at the higher core-to-Rydberg excitations is most likely due to soft x-ray emission processes that are followed by autoionization. The results also suggest that resonant Auger decay from the core–valence doubly excited states contributes to the N+2 ion yield at the photon energies that are located on both sides of the N 1s ionization limit.

Optimization of multijunction solar cells through indoor energy yield measurements

The variability of the solar spectra in the field may reduce the annual energy yield of multijunction solar cells. It would, therefore, be desirable to implement a cell design procedure based on the maximization of the annual energy yield. In this study, we present a measurement technique to generate maps of the real performance of the solar cell for a range of light spectrum contents using a solar simulator with a computer-controllable spectral content. These performance maps are demonstrated to be a powerful tool for analyzing the characteristics of any given set of annual spectra representative of a site and their influence on the energy yield of any solar cell. The effect of luminescence coupling on buffering against variations of the spectrum and improving the annual energy yield is demonstrated using this method.

Kinetics of color center formation in silica irradiated with swift heavy ions: Thresholding and formation efficiency

We have determined the cross-section σ for color center generation under single Br ion impacts on amorphous SiO2. The evolution of the cross-sections, σ(E) and σ(Se), show an initial flat stage that we associate to atomic collision mechanisms. Above a certain threshold value (Se > 2 keV/nm), roughly coinciding with that reported for the onset of macroscopic disorder (compaction), σ shows a marked increase due to electronic processes. In this regime, a energetic cost of around 7.5 keV is necessary to create a non bridging oxygen hole center-E′ (NBOHC/E′) pair, whatever the input energy. The data appear consistent with a non-radiative decay of self-trapped excitons.

Policy processes and collective action in water reforms: the cases of Nicaragua and Suriname

Las reformas de agua en países en desarrollo suelen llevarse a cabo junto con cambios institucionales más profundos o, incluso, acompañadas de cambios constitucionales o de régimen político. Por lo tanto, los marcos institucionales adaptados a países gobernados sujetos al estado de derecho pueden no ser apropiados para contextos gobernados fundamentalmente, al menos en sus inicios, por instituciones informales o poco maduras. Esta tesis toma las reformas de agua como punto de partida y pretende contribuir a la literatura mediante una serie de análisis empíricos tanto del ámbito general como del plano individual o sujeto personal de la política del agua. En el ámbito general, el foco se pone en los factores que explican el fallo de la acción colectiva en dos contextos diferentes: 1) en la implementación de la nueva Ley de Aguas de Nicaragua y 2) en el mantenimiento y revitalización de las instituciones de riego en Surinam. En el plano del individuo, la investigación se centra en las decisiones de los usuarios de los recursos y analiza el papel crítico de las variables sociales para la gestión de los recursos comunes. Para ello, el método de investigación utilizado es mixto, combinando el análisis de entrevistas, encuestas y experimentos. En el ámbito general, los resultados muestran que las principales barreras para la implementación de la nueva Ley de Aguas de Nicaragua podrían tener su reflejo en el lenguaje de la Ley y, por tanto, en la forma en la que se definen y configuran las instituciones incluidas en dicha Ley. Así, la investigación demuestra que la implementación de políticas no puede ser estudiada o entendida sin tener en cuenta tanto el diseño de la propia política como el marco socio-ecológico en el que se enmarca. El contexto específico de Nicaragua remarca la importancia de considerar tanto las instituciones formales como informales en los procesos de transición política. A pesar de que las reformas de agua requieren plazos largos para su implementación, el hecho de que exista una diferencia entre las reglas tal cual se definen formalmente y las reglas que operan en la realidad merece una mayor consideración en el diseño de políticas basadas fundamentalmente en instituciones formales. En el ámbito de la conducta individual, el análisis de la acción colectiva ofrece una serie de observaciones empíricas interesantes. En el caso de Nicaragua, los resultados indican que la intensidad de las relaciones sociales, el tipo de agentes dispuestos a proporcionar apoyo social y el nivel de confianza en la comunidad son factores que explican de manera significativa la participación en la comunidad. Sin embargo, el hecho de que la gestión colectiva de riego se produzca, en la mayoría de casos, en torno a lazos familiares sugiere que las variables de capital social críticas se definen en gran medida en la esfera familiar, siendo difícil que se extiendan fuera de estos nexos. El análisis experimental de los resultados de un juego de uso de recurso común y contribución al bien público muestra que las preferencias pro-sociales de los individuos y la heterogeneidad del grupo en términos de composición por sexo son factores que explican significativamente los resultados y las decisiones de apropiación a lo largo del juego. En términos del diseño de las políticas, es fundamental tener en cuenta las dinámicas de participación y uso de los recursos comunes de manera que los niveles de cooperación puedan mantenerse en el largo plazo, lo cual, como se observa en el caso de Surinam, no es siempre posible. Finalmente, el caso de Surinam es un ejemplo ilustrativo de los procesos de acción colectiva en economías en transición. El análisis del fallo de la acción colectiva en Surinam muestra que los procesos políticos vinculados al período colonial y de independencia explican en gran medida la falta de claridad en las reglas operacionales y colectivas que gobiernan la gestión de los sistemas de riego y drenaje. Los resultados empíricos sugieren que a pesar de que la acción colectiva para la provisión de los servicios de riego y drenaje estaba bien establecida bajo el régimen colonial, la auto-organización no prosperó en un contexto dependiente del apoyo externo y regido fundamentalmente por reglas diseñadas al nivel competencial del gobierno central. El sistema socio-ecológico que se desarrolló durante la transición post-colonial favoreció, así, la emergencia de comportamientos oportunistas, y posteriormente la inoperancia de los Water Boards (WBs) creados en la época colonial. En este sentido, cualquier intento por revitalizar los WBs y fomentar el desarrollo de la auto-organización de los usuarios necesitará abordar los problemas relacionados con los patrones demográficos, incluyendo la distribución de la tierra, el diseño de instituciones y la falta de confianza en el gobierno, además de las inversiones típicas en infraestructura y sistemas de información hidrológicos. El liderazgo del gobierno, aportando empuje de arriba-abajo, es, además, otro elemento imprescindible en Surinam. ABSTRACT Water reforms in developing countries take place along deeper institutional and even constitutional. Therefore, institutional frameworks that might result in positive outcomes in countries governed by the rule of law might not fit in contexts governed mainly by informal or immature institutions. This thesis takes water reforms as the starting point and aims to contribute to the literature by presenting several conceptual and empirical analyses at both general and individual levels. At the general national level, the focus is on the factors explaining failure of collective action in two different settings: 1) in the implementation of the new Nicaraguan Water Law and 2) in sustaining and revitalizing irrigation institutions in Suriname. At the individual level, the research focuses on the actions of resource users and analyzes the critical role of social variables for common pool resources management. For this purpose, the research presented in this thesis makes use of a mixed-method approach, combining interviews, surveys and experimental methods. Overall, the results show that major barriers for the implementation of the new Nicaraguan Water Law have its reflection on the language of the Law and, therefore, on the way institutions are defined and configured. In this sense, our study shows that implementation cannot fruitfully be studied and understood without taking into account both the policy design and the social-ecological context in which it is framed. The specific setting of Nicaragua highlights the relevance of considering both formal and informal institutions when promoting policy transitions. Despite the unquestionable fact that water reforms implementation needs long periods of time, there is still a gap between the rules on paper and the rules on the ground that deserves further attention when proposing policy changes on the basis of formal institutions. At the level of the individual agent, the analysis of collective action provides a number of interesting empirical insights. In the case of Nicaragua, I found that the intensity of social networks, the type of agents willing to provide social support and the level of trust in the community are all significant factors in explaining collective action at community level. However, the fact that most collective irrigation relies on family ties suggests that critical social capital variables might be defined within the family sphere and making it difficult to go beyond it. Experimental research combining a common pool resource and a public good game in Nicaragua shows that individuals’ pro-social traits and group heterogeneity in terms of sex composition are significant variables in explaining efficiency outcomes and effort decisions along the game. Thus, with regard to policy design, it is fundamental to consider carefully the dynamics of agents' participation and use of common pool resources, for sustaining cooperation in the long term, which, as seen in the case and Surinam, is not always possible. The case of Suriname provides a rich setting for the analysis of collective action in transition economies. The analysis of decay of collective irrigation in Suriname shows that the lack of clear operational and collective choice rules appear to be rooted in deeper political processes that date back to the colonial period. The empirical findings suggest that despite collective action for the provision of irrigation and drainage services was well established during the colonial period, self-organization did not flourish in a context governed by colonial state-crafted rules and mostly dependent on external support. The social-ecological system developed during the post-colonial transition process favored the emergence of opportunistic behavior. In this respect, any attempt to revitalize WBs and support self-organization will need to tackle the problems derived from demographic patterns, including land allocation, institutions design and government distrust, in addition to the typical investments in both physical infrastructure and hydrological information systems. The leadership role of the government, acting as a top-down trigger, is another essential element in Suriname.

Preliminary mineralogy and ore petrology of the intermediate-sulfidation pallancata deposit, Ayacucho, Peru

Se investiga la compleja mineralogía del Yacimiento de Pallancata (6º productor de plata del mundo) y se establecen las condiciones de formación (P.T) basadas en la petrología de las menas comparada con los datos de mineralogía experimental y en la petrografía y microtermometría de inclusiones fluídas en la ganga silicatada, resultando un depósito típicamente caracterizado como epitermal de sulfuración intermedia.ABSTRACT:Pallancata is a world-class intermediate-sulfidation epithermal deposit, hosted by upper Miocene volcanics of the south-central Peruvian Andes in a sinuous N70ºW, ∼75º SW strike-slip structure, with wide (up to 35 m) pull-apart dilation zones related to bends of the vein strike. The structural evolution of the vein from earlier brecciation to later open space infill resembles the Shila Paula district (Chauvet et al. 2006). Fluid inclusion petrography and microthermometry show that ore deposition is related to protracted boiling of very diluted, mainly meteoric fluids, starting at 250–260 ºC, under ∼300 m hydrostatic head. The mineralogical-petrological study reveals a complex sequence of mineralization (eight stages) and mineral reactions consistent with Ag2S enrichment or Sb2S3 depletion, or both, during cooling over the temperature range 250–200 ºC: pyrite, sphalerite, galena, miargyrite, pyrargyrite-proustite, chalcopyrite, polybasite-pearceite, argentite (now acanthite), and Au–Ag alloy (“electrum”). This Ag2S enrichment and Sb2S3depletion during cooling may be explained by decay of a Ag-rich galena precursor at deeper levels (Pb2S2–AgSbS2 solid solution), which rapidly becomes unstable with decreasing temperature, producing residual (stoichiometric) PbS and more mobile Ag and Sb sulfide phases, which migrated upward and laterally away from the thermal core of the system. The core is still undisclosed by mining works, but the available geochemical evidence (logAg/log Pb ratios decreasing at depth) is consistent with this interpretation, implying a deeper potential resource. Data from sulfide geothermometry, based on mineral equilibria, document the thermal evolution of the system below 200 ºC (stephanite, uytenbogaardtite, jalpaite, stromeyerite, mckinstryite, among others). The end of the most productive stages (3, 4, and 5) is marked by the precipitation of stephanite at temperatures below 197 ± 5 ºC, but precipitation of residual silver continues through the waning stages of the hydrothermal system down to <93.3 ºC (stromeyerite) or in a supergene redistribution (stage 8, acanthite II).

First steps of Roman Cement in Spain

Natural cement was patented in 1796 but it didn’t arrive in Spain until 1835. No one knows exactly where the production started in Spain, because it emerged independently at the same time in many places. Most of these outbreaks are concentrated in the north and northwest of Spain: Basque Country (Zumaya and Rezola) and Catalonia (San Celoní and San Juan de las Abadesas).Natural cement was extensively used to decorate historical buildings during the nineteenth and beginning of twentieth century in Madrid. It was the building material which realised the architects and builders dreams of mass-produced cast elements in a wide variety of styles. Its arrival replaced traditional materials that were used previously (lime, gypsum and hydraulic limes). However, its use was not extended in time, and soon it was replaced by the use of artificial Portland cements. During 20th century this building material disappeared from use. What remains is it’s memory, in thousands and thousands of “stone witnesses” in our cities. Final properties of the cement largely depend on raw materials used and its combustion temperature. However, it was characterised by an easily implementation on facade masonry, fast-setting (about 15 minutes), good resistance , an agreeable structural consistency and colour.This article aims to show first steps, evolution and decay of Natural Cement Industry in Spain and its application in Madrid.

Surface InGaAs nanostructures for sensing applications

El desarrollo de sensores está ganando cada vez mayor importancia debido a la concienciación ciudadana sobre el medio ambiente haciendo que su desarrollo sea muy elevado en todas las disciplinas, entre las que cabe destacar, la medicina, la biología y la química. A pesar de la existencia de estos dispositivos, este área está aún por mejorar, ya que muchos de los materiales propuestos hasta el momento e incluso los ya comercializados muestran importantes carencias de funcionamiento, eficiencia e integrabilidad entre otros. Para la mejora de estos dispositivos, se han propuesto diversas aproximaciones basadas en nanosistemas. Quizá, uno de las más prometedoras son las nanoestructuras de punto cuántico, y en particular los semiconductores III-V basados en la consolidada tecnología de los arseniuros, las cuáles ofrecen excelentes propiedades para su uso como sensores. Además, estudios recientes demuestran su gran carácter sensitivo al medio ambiente, la posibilidad de funcionalizar la superficie para la fabricación de sensores interdisciplinares y posibilididad de mejorar notablemente su eficiencia. A lo largo de esta tesis, nos centramos en la investigación de SQD de In0.5Ga0.5As sobre substratos de GaAs(001) para el desarrollo de sensores de humedad. La tesis abarca desde el diseño, crecimiento y caracterización de las muestras hasta la el posterior procesado y caracterización de los dispositivos finales. La optimización de los parámetros de crecimiento es fundamental para conseguir una nanoestructura con las propiedades operacionales idóneas para un fin determinado. Como es bien sabido en la literatura, los parámetros de crecimiento (temperatura de crecimiento, relación de flujos del elemento del grupo V y del grupo I II (V/III), velocidad de crecimiento y tratamiento térmico después de la formación de la capa activa) afectan directamente a las propiedades estructurales, y por tanto, operacionales de los puntos cuánticos (QD). En esta tesis, se realiza un estudio de las condiciones de crecimiento para el uso de In0.5Ga0.5As SQDs como sensores. Para los parámetros relacionados con la temperatura de crecimiento de los QDs y la relación de flujos V / I I I se utilizan los estudios previamente realizados por el grupo. Mientras que este estudio se centrará en la importancia de la velocidad de crecimiento y en el tratamiento térmico justo después de la nucleación de los QDs. Para ello, se establece la temperatura de creciemiento de los QDs en 430°C y la relación de flujos V/III en 20. Como resultado, los valores más adecuados que se obtienen para la velocidad de crecimiento y el tratamiento térmico posterior a la formación de los puntos son, respectivamente, 0.07ML/s y la realización de una bajada y subida brusca de la temperatura del substrato de 100°C con respecto a la temperatura de crecimiento de los QDs. El crecimiento a una velocidad lo suficientemente alta que permita la migración de los átomos por la superficie, pero a su vez lo suficientemente baja para que se lleve a cabo la nucleación de los QDs; en combinación con el tratamiento brusco de temperatura que hace que se conserve la forma y composición de los QDs, da lugar a unos SQDs con un alto grado de homogeneidad y alta densidad superficial. Además, la caracterización posterior indica que estas nanoestructuras de gran calidad cristalina presentan unas propiedades ópticas excelentes incluso a temperatura ambiente. Una de las características por la cual los SQD de Ino.5Gao.5As se consideran candidatos prometedores para el desarrollo de sensores es el papel decisivo que juega la superficie por el mero hecho de estar en contacto directo con las partículas del ambiente y, por tanto, por ser capaces de interactuar con sus moléculas. Así pues, con el fin de demostrar la idoneidad de este sistema para dicha finalidad, se evalúa el impacto ambiental en las propiedades ópticas y eléctricas de las muestras. En un primer lugar, se analiza el efecto que tiene el medio en las propiedades ópticas. Para dicha evaluación se compara la variación de las propiedades de emisión de una capa de puntos enterrada y una superficial en distintas condiciones externas. El resultado que se obtiene es muy claro, los puntos enterrados no experimentan un cambio óptico apreciable cuando se varían las condiciones del entorno; mientras que, la emisión de los SQDs se modifica significativamente con las condiciones del medio. Por una parte, la intensidad de emisión de los puntos superficiales desaparece en condiciones de vacío y decrece notablemente en atmósferas secas de gases puros (N2, O2). Por otra parte, la fotoluminiscencia se conserva en ambientes húmedos. Adicionalmente, se observa que la anchura a media altura y la longitud de onda de emisión no se ven afectadas por los cambios en el medio, lo que indica, que las propiedades estructurales de los puntos se conservan al variar la atmósfera. Estos resultados apuntan directamente a los procesos que tienen lugar en la superficie entre estados confinados y superficiales como responsables principales de este comportamiento. Así mismo, se ha llevado a cabo un análisis más detallado de la influencia de la calidad y composición de la atmósfera en las propiedades ópticas de los puntos cuánticos superficiales. Para ello, se utilizan distintas sustancias con diferente polaridad, composición atómica y masa molecular. Como resultado se observa que las moléculas de menor polaridad y más pesadas causan una mayor variación en la intensidad de emisión. Además, se demuestra que el oxígeno juega un papel decisivo en las propiedades ópticas. En presencia de moléculas que contienen oxígeno, la intensidad de fotoluminiscencia disminuye menos que en atmósferas constituidas por especies que no contienen oxígeno. Las emisión que se observa respecto a la señal en aire es del 90% y del 77%, respectivamente, en atmósferas con presencia o ausencia de moléculas de oxígeno. El deterioro de la señal de emisión se atribuye a la presencia de defectos, enlaces insaturados y, en general, estados localizados en la superficie. Estos estados actúan como centros de recombinación no radiativa y, consecuentemente, se produce un empeoramiento de las propiedades ópticas de los SQDs. Por tanto, la eliminación o reducción de la densidad de estos estados superficiales haría posible una mejora de la intensidad de emisión. De estos experimentos de fotoluminiscencia, se deduce que las interacciones entre las moléculas presentes en la atmósfera y la superficie de la muestra modifican la superficie. Esta alteración superficial se traduce en un cambio significativo en las propiedades de emisión. Este comportamiento se atribuye a la posible adsorción de moléculas sobre la superficie pasivando los centros no radiativos, y como consecuencia, mejorando las propiedades ópticas. Además, los resultados demuestran que las moléculas que contienen oxígeno con mayor polaridad y más ligeras son adsorbidas con mayor facilidad, lo que hace que la intensidad óptica sufra variaciones despreciables con respecto a la emisión en aire. Con el fin de desarrollar sensores, las muestras se procesan y los dispositivos se caracterizan eléctricamente. El procesado consiste en dos contactos cuadrados de una aleación de Ti/Au. Durante el procesado, lo más importante a tener en cuenta es no realizar ningún ataque o limpieza que pueda dañar la superficie y deteriorar las propiedades de las nanostructuras. En este apartado, se realiza un análisis completo de una serie de tres muestras: GaAs (bulk), un pozo cuántico superficial (SQW) de Ino.5Gao.5As y SQDs de Ino.5Gao.5As. Para ello, a cada una de las muestras se le realizan medidas de I-V en distintas condiciones ambientales. En primer lugar, siguiendo los resultados obtenidos ópticamente, se lleva a cabo una comparación de la respuesta eléctrica en vacío y aire. A pesar de que todas las muestras presentan un carácter más resistivo en vacío que en aire, se observa una mayor influencia sobre la muestra de SQD. En vacío, la resistencia de los SQDs decrece un 99% respecto de su valor en aire, mientras que la variación de la muestras de GaAs e Ino.5Gao.5As SQW muestran una reducción, respectivamente, del 31% y del 20%. En segundo lugar, se realiza una evaluación aproximada del posible efecto de la humedad en la resistencia superficial de las muestras mediante la exhalación humana. Como resultado se obtiene, que tras la exhalación, la resistencia disminuye bruscamente y recupera su valor inicial cuando dicho proceso concluye. Este resultado preliminar indica que la humedad es un factor crítico en las propiedades eléctricas de los puntos cuánticos superficiales. Para la determinación del papel de la humedad en la respuesta eléctrica, se somete a las muestras de SQD y SQW a ambientes con humedad relativa (RH, de la siglas del inglés) controlada y se analiza el efecto sobre la conductividad superficial. Tras la variación de la RH desde 0% hasta el 70%, se observa que la muestra SQW no cambia su comportamiento eléctrico al variar la humedad del ambiente. Sin embargo, la respuesta de la muestra SQD define dos regiones bien diferenciadas, una de alta sensibilidad para valores por debajo del 50% de RH, en la que la resistencia disminuye hasta en un orden de magnitud y otra, de baja sensibilidad (>50%), donde el cambio de la resistencia es menor. Este resultado resalta la especial relevancia no sólo de la composición sino también de la morfología de la nanostructura superficial en el carácter sensitivo de la muestra. Por último, se analiza la influencia de la iluminación en la sensibilidad de la muestra. Nuevamente, se somete a las muestras SQD y SQW a una irradiación de luz de distinta energía y potencia a la vez que se varía controladamente la humedad ambiental. Una vez más, se observa que la muestra SQW no presenta ninguna variación apreciable con las alteraciones del entorno. Su resistencia superficial permanece prácticamente inalterable tanto al modificar la potencia de la luz incidente como al variar la energía de la irradiación. Por el contrario, en la muestra de SQD se obtiene una reducción la resistencia superficial de un orden de magnitud al pasar de condiciones de oscuridad a iluminación. Con respecto a la potencia y energía de la luz incidente, se observa que a pesar de que la muestra no experimenta variaciones notables con la potencia de la irradiación, esta sufre cambios significativos con la energía de la luz incidente. Cuando se ilumina con energías por encima de la energía de la banda prohibida (gap) del GaAs (Eg ~1.42 eV ) se produce una reducción de la resistencia de un orden de magnitud en atmósferas húmedas, mientras que en atmósferas secas la conductividad superficial permanece prácticamente constante. Sin embargo, al inicidir con luz de energía menor que Eg, el efecto que se produce en la respuesta eléctrica es despreciable. Esto se atribuye principalmente a la densidad de portadores fotoactivados durante la irradiación. El volumen de portadores excita dos depende de la energía de la luz incidente. De este modo, cuando la luz que incide tiene energía menor que el gap, el volumen de portadores generados es pequeño y no contribuye a la conductividad superficial. Por el contrario, cuando la energía de la luz incidente es alta (Eg), el volumen de portadores activados es elevado y éstos contribuyen significantemente a la conductividad superficial. La combinación de ambos agentes, luz y humedad, favorece el proceso de adsorción de moléculas y, por tanto, contribuye a la reducción de la densidad de estados superficiales, dando lugar a una modificación de la estructura electrónica y consecuentemente favoreciendo o dificultando el transporte de portadores. ABSTRACT Uncapped three-dimensional (3D) nanostructures have been generally grown to assess their structural quality. However, the tremendous growing importance of the impact of the environment on life has become such nanosystems in very promising candidates for the development of sensing devices. Their direct exposure to changes in the local surrounding may influence their physical properties being a perfect sign of the atmosphere quality. The goal of this thesis is the research of Ino.5Gao.5As surface quantum dots (SQDs) on GaAs(001), covering from their growth to device fabrication, for sensing applications. The achievement of this goal relies on the design, growth and sample characterization, along with device fabrication and characterization. The first issue of the thesis is devoted to analyze the main growth parameters affecting the physical properties of the Ino.5Gao.5As SQDs. It is well known that the growing conditions (growth temperature , deposition rate, V/III flux ratio and treatment after active layer growth) directly affect the physical properties of the epilayer. In this part, taking advantage of the previous results in the group regarding Ino.5Gao.5As QD growth temperature and V/III ratio, the effect of the growth rate and the temperature treatment after QDs growth nucleation is evaluated. Setting the QDs growth temperature at 430°C and the V/III flux ratio to ~20, it is found that the most appropriate conditions rely on growing the QDs at 0.07ML/s and just after QD nucleation, rapidly dropping and again raising 100°C the substrate temperature with respect to the temperature of QD growth. The combination of growing at a fast enough growth rate to promote molecule migration but sufficiently slow to allow QD nucleation, together with the sharp variation of the temperature preserving their shape and composition yield to high density, homogeneous Ino.5Gao.5As SQDs. Besides, it is also demonstrated that this high quality SQDs show excellent optical properties even at room temperature (RT). One of the characteristics by which In0.5Ga0.5As/GaAs SQDs are considered promising candidates for sensing applications is the crucial role that surface plays when interacting with the gases constituting the atmosphere. Therefore, in an attempt to develop sensing devices, the influence of the environment on the physical properties of the samples is evaluated. By comparing the resulting photoluminescence (PL) of SQDs with buried QDs (BQDs), it is found that BQDs do not exhibit any significant variation when changing the environmental conditions whereas, the external conditions greatly act on the SQDs optical properties. On one hand, it is evidenced that PL intensity of SQDs sharply quenches under vacuum and clearly decreases under dry-pure gases atmospheres (N2, O2). On the other hand, it is shown that, in water containing atmospheres, the SQDs PL intensity is maintained with respect to that in air. Moreover, it is found that neither the full width at half maximun nor the emission wavelength manifest any noticeable change indicating that the QDs are not structurally altered by the external atmosphere. These results decisively point to the processes taking place at the surface such as coupling between confined and surface states, to be responsible of this extraordinary behavior. A further analysis of the impact of the atmosphere composition on the optical characteristics is conducted. A sample containing one uncapped In0.5Ga0.5As QDs layer is exposed to different environments. Several solvents presenting different polarity, atomic composition and molecular mass, are used to change the atmosphere composition. It is revealed that low polarity and heavy molecules cause a greater variation on the PL intensity. Besides, oxygen is demonstrated to play a decisive role on the PL response. Results indicate that in presence of oxygen-containing molecules, the PL intensity experiments a less reduction than that suffered in presence of nonoxygen-containing molecules, 90% compared to 77% signal respect to the emission in air. In agreement with these results, it is demonstrated that high polarity and lighter molecules containing oxygen are more easily adsorbed, and consequently, PL intensity is less affected. The presence of defects, unsaturated bonds and in general localized states in the surface are proposed to act as nonradiative recombination centers deteriorating the PL emission of the sample. Therefore, suppression or reduction of the density of such states may lead to an increase or, at least, conservation of the PL signal. This research denotes that the interaction between sample surface and molecules in the atmosphere modifies the surface characteristics altering thus the optical properties. This is attributed to the likely adsoption of some molecules onto the surface passivating the nonradiative recombination centers, and consequently, not deteriorating the PL emission. Aiming for sensors development, samples are processed and electrically characterized under different external conditions. Samples are processed with two square (Ti/Au) contacts. During the processing, especial attention must be paid to the surface treatment. Any process that may damage the surface such as plasma etching or annealing must be avoided to preserve the features of the surface nanostructures. A set of three samples: a GaAs (bulk), In0.5Ga0.5As SQDs and In0.5Ga0.5As surface quantum well (SQW) are subjected to a throughout evaluation. I-V characteristics are measured following the results from the optical characterization. Firstly, the three samples are exposed to vacuum and air. Despite the three samples exhibit a more resistive character in vacuum than in air, it is revealed a much more clear influence of the pressure atmosphere in the SQDs sample. The sheet resistance (Rsh) of SQDs decreases a 99% from its response value under vacuum to its value in air, whereas Rsh of GaAs and In0.5Ga0.5As SQW reduces its value a 31% and a 20%, respectively. Secondly, a rough analysis of the effect of the human breath on the electrical response evidences the enormous influence of moisture (human breath is composed by several components but the one that overwhelms all the rest is the high concentration of water vapor) on the I-V characteristics. Following this result, In0.5Ga0.5As SQDs and In0.5Ga0.5As SQW are subjected to different controlled relative humidity (RH) environments (from 0% to 70%) and electrically characterized. It is found that SQW shows a nearly negligible Rsh variation when increasing the RH in the surroundings. However, the response of SQDs to changes in the RH defines two regions. Below 50%, high sensitive zone, Rsh of SQD decreases by more than one order of magnitude, while above 50% the dependence of Rsh on the RH becomes weaker. These results remark the role of the surface and denote the existence of a finite number of surface states. Nevertheless, most significantly, they highlight the importance not only of the material but also of the morphology. Finally, the impact of the illumination is determined by means of irradiating the In0.5Ga0.5As SQDs and In0.5Ga0.5As SQW samples with different energy and power sources. Once again, SQW does not exhibit any correlation between the surface conductivity and the external conditions. Rsh remains nearly unalterable independently of the energy and power of the incident light. Conversely, Rsh of SQD experiences a decay of one order of magnitude from dark-to-photo conditions. This is attributed to the less density of surface states of SQW compared to that of SQDs. Additionally, a different response of Rsh of SQD with the energy of the impinging light is found. Illuminating with high energy light results in a Rsh reduction of one order of mag nitude under humid atmospheres, whereas it remains nearly unchanged under dry environments. On the contrary, light with energy below the bulk energy bandgap (Eg), shows a negligible effect on the electrical properties regardless the local moisture. This is related to the density of photocarriers generated while lighting up. Illuminating with excitation energy below Eg affects a small absorption volume and thus, a low density of photocarriers may be activated leading to an insignificant contribution to the conductivity. Nonetheless, irradiating with energy above the Eg can excite a high density of photocarriers and greatly improve the surface conductivity. These results demonstrate that both illumination and humidity are therefore needed for sensing. The combination of these two agents improves the surface passivation by means of molecule adsorption reducing the density of surface states, thus modifying the electronic structures, and consequently, promoting the carrier motion.

Nutritive value for ruminants of winter oats-legume intercrops in organic cultivation

Winter oats were grown according to European organic farming regulations in monoculture (oats) and in intercropping with bard vetch (BAV), bitter vetch (BIV) or both legumes (MIX) to evaluate the effects of intercropping on forage yield and nutritive value for ruminants. The experiment was carried out as a randomised complete block design with four replications, and whole forage samples were obtained at two harvest dates (June and July). For both harvest times, all intercrops increased (P < 0.05) forage yield compared with oats, but forage crude protein content was only increased (P < 0.05) for BAV and MIX. Compared with oats, intercropping with BAV increased (P < 0.05) in vitro rate of gas production and total volatile fatty acid production, indicating a higher rate and extent of rumen degradation of BAV forage. In contrast, BIV forage harvested in June had lower (P < 0.05) rate of gas production and total volatile fatty acid production than June oats, but in general no differences in the in vitro rumen fermentation were detected between oats and BIV samples harvested in July. The results indicate that forage yield and quality can be enhanced by intercropping oats with BAV; however, intercropping with BIV increased yield but decreased nutritive value of the forage.

Approach to the potential production of giant reed in surplus saline lands of Spain

Growing energy crops on marginal land has been promoted as a way of ensuring that biomass production involves an acceptable and sustainable use of land. Saline and saline-prone agricultural lands represent an opportunity for growing energy crops avoiding the displacement of food production and contributing to restoration of degraded land. Giant reed (Arundo donax L.) is a perennial grass that has been proposed as a promising energy crop for lignocellulosic biomass production while its tolerance to salinity has been proved. In this work, the identification of surplus saline lands that could be irrigated with saline waters for growing tolerant-energy crops (giant reed) in the mainland of Spain and the assessment of the agronomically attainable yield in these limiting growing conditions were undertaken. To this purpose, a GIS analysis was conducted using geodatabases related to saline areas, agro-climatic conditions, irrigation water requirements, agricultural land availability, restrictions regarding the range of electrical conductivity tolerated by the crop, competition with agro-food crops and irrigation water provisions. According to the approach developed, the irrigated and saline agricultural area available and suitable for biomass production from giant reed amounted up to 34 412 ha. The agronomically attainable yield in these limiting conditions was estimated at 12.7 – 22.2 t dm ha−1 yr−1 and the potential production of lignocellulosic biomass, 597 338 t dm yr−1. The methodology followed in this study can be applied to other target regions; it allows the identification of this type of marginal lands, where salinity-tolerant plant species could be grown for bioenergy purposes, avoiding competition with agro-food crops, and where soil restoration measurements should be undertaken.